JP6860486B2 - Magnetic core based on nanocrystalline magnetic alloy - Google Patents

Description

[0001] Aspects of the present invention relate to magnetic cores based on nanocrystalline magnetic alloys with high saturated magnetic induction, low coercive force and low iron loss.

[0002] Crystalline silicon steel, ferrite, cobalt-based amorphous soft magnetic alloys, iron-based amorphous alloys and nanocrystalline alloys are derived magnetic meters, electric choke coils, pulse power supplies, transformers. It has been widely used in appliances, motors, generators, current sensors, magnetic cores for antennas and electromagnetic wave blocking sheets. Silicon steel widely used are inexpensive, exhibit high saturation induction B _S, however, it is often lost at high frequency. One reason for high magnetic losses, their coercivity H _C is higher and about 8A / m. Ferrites have a low saturation magnetic lead and are therefore magnetically saturated when used in high power inductive magnetometers. Cobalt-based amorphous alloys are relatively expensive and usually result in saturated magnetic induction of less than 1T. Magnetic member made from an amorphous alloy of cobalt-based, due to their low saturation induction, low levels of operation magnetic induction (which is lower than the saturation induction B _S) is large in order to compensate for the There is a need. Amorphous alloy of the iron-based has a _{B S} of 1.5～1.6T, which is lower than the _{B S} of about 2T for silicon steel. Energy efficient for the apparatus described above, to produce the core of a small size, magnetic alloy having a coercive force H _C of less than saturation induction and 8A / m of greater than 1.6T can be clearly needed ing.

[0003] Iron-based nanocrystalline alloys with high saturated magnetic induction and low coercive force are taught in WO2007 / 032531 (hereinafter referred to as "'531") of the international application. This _{alloy, Fe 100-x-y-} z Cu x B y X z (X: Si, S, C, P, Al, Ge, Ga, and at least one from the group consisting of Be) (wherein, For x, y, z, it has a chemical composition of 0.1 ≦ x ≦ 3, 10 ≦ y ≦ 20, 0 <z ≦ 10, and 10 <y + z ≦ 24 (all atomic percentages)) and less than 60 nm. It has a local structure in which crystalline particles with an average diameter are dispersed and occupy more than 30 percent by volume of the alloy. This alloy contains copper, but its technical role in the alloy has not been clearly demonstrated. As of '531, the copper atoms formed clusters of atoms provided as seeds for the nanocrystals, which were increased in size by heat treatment after the material was made, thereby causing '531. It was thought that it would have the local structure defined in the publication. In addition, copper clusters can be present in the molten alloy because the heat of copper mixing becomes positive with iron according to common metallurgical rules, which is above copper in the molten alloy. Was thought to determine the content of. However, it was later revealed that during rapid solidification, copper reached its solid solution limit, which caused it to precipitate and initiate the process of nanocrystallization. Under supercooled conditions, the copper content x is 1.2 and 1 to achieve the assumed local atomic structure that allows early nanocrystallization during rapid solidification. Must be between .6. Therefore, the range of copper content of 0.1 ≦ x ≦ 3 in '531 is greatly reduced. In this application, these alloys are classified as P-type alloys. In fact, the alloys of '53 1A were found to be brittle due to partial crystallization, and thus the resulting magnetic properties were acceptable but difficult to handle. In addition, it was found that casting a stable material was difficult because the conditions for rapid solidification of the alloys published in '53 1 changed greatly depending on the solidification rate. Therefore, improvements beyond the products of '53 1A are desired.

International release WO2007 / 032531

[0004] In the process of improvement over the products of '531, fine nanocrystals by rapidly heating the alloy according to aspects of the invention, which first has fine crystal particles that are not cast. It was found that a structure was formed. It was also found that the heat-treated alloy exhibited excellent soft magnetic properties such as high saturated magnetic induction exceeding 1.7T. Alloys exhibiting these magnetic properties are referred to as Q-type alloys in this application. The mechanism of nanocrystallization in a Q-type alloy according to aspects of the present invention is an amorphous phase formed in the alloy during crystallization by replacing glass-forming elements such as P and Nb with other elements. It differs from the mechanism of alloys in related technical fields (see, eg, US Pat. No. 8007600 and International Patent Publication No. WO 2008/133301) in that it improves the thermal stability of. Furthermore, elemental substitution suppresses the growth of crystalline particles that precipitate during the heat treatment. In addition, the rapid heating of the alloy ribbon reduces the rate of diffusion of atoms in the material, resulting in a reduced number of crystal nucleation positions. It is difficult for the element P found in P-type alloys to maintain its purity in the material, and P tends to diffuse at temperatures below 300 ° C., thereby reducing the thermal stability of the alloy. .. Therefore, P is not a desirable element in this alloy. Elements such as Nb and Mo are known to improve the formability of Fe-based alloys in the vitreous or amorphous state, but they are non-magnetic and their atomic size is large. Therefore, it tends to reduce the saturated magnetic induction of the alloy. Therefore, in the desired alloy, the content of elements such as Nb and Mo should be as low as possible.

[0005] The growth of large microcrystals during heat treatment, often encountered in products of the relevant technical field, is mitigated in ribbon-like materials, but in laminated or toroidal cores (toroidal cores). For magnetic cores with such large dimensions, uniform heat treatment must be guaranteed.

[0006] Therefore, one aspect of the present invention is to increase the heating rate during heat treatment of the alloy, thereby reducing magnetic loss such as iron core loss in nanocrystallized materials and having improved performance. It is to develop a process that can obtain the parts.

[0007] One major aspect of the present invention is to provide an optimally heat treated alloy-based magnetic core according to aspects of the invention for the purpose of using the magnetic core in transformers and induction magnetometers in power generation and management. That is.

[0008] Considering all the effects of the component elements described in the previous paragraph, the alloy may have a chemical composition of FeCu _x B _y Si _z, where, 0.6 ≦ x <1.2, 10 ≦ y ≦ 20, 0 <z ≦ 10, 10 ≦ (y + z) ≦ 24, the numerical value is atomic percent, and the balance is Fe and additives of various selective elements described later in the present disclosure. The alloy can be cast into a ribbon , for example, by the rapid solidification method taught in US Pat. No. 4,142,571.

[0009] A rapidly solidified ribbon with the chemical composition shown in the previous paragraph first brings the ribbon into direct contact with a metal or ceramic surface at a temperature between 450 ° C and 550 ° C, then 10 ° C / sec. The heat treatment can be performed by rapidly heating the ribbon to above 300 ° C. at a higher heating rate.

[0010] The heat treatment in the previous paragraph shall be performed either in a zero magnetic field or in a predetermined magnetic field applied along the length or width of the ribbon, depending on the intended use. Can be done.

[0011] In the heat treatment process described above, nanocrystals with an average particle size of less than 40 nm are dispersed in an amorphous matrix, and those nanocrystals occupy more than 30 volume percent. To generate such a local structure.

[0012] heat-treated ribbon according to the previous paragraph, the magnetic induction of more than 1.6T at 80A / m, has a coercive force _{H C} of less than saturation induction and 6.5A / m exceeds 1.7 T. In addition, this heat treated ribbon exhibited a core loss of less than 0.4 W / kg at 1.6 T and 50 Hz and a core loss of less than 0.55 W / kg at 1.6 T and 60 Hz.

[0013] The heat-treated ribbon is wound into a toroid-like magnetic core, and then with or without a magnetic field applied along the length direction of the ribbon, at 400 ° C. to 500 ° C. for 1 minute. It can be heat treated for ~ 8 hours. Such an annealing procedure involving a magnetic field is referred to in the present disclosure as longitudinal magnetic field annealing. When the ribbon is wound so as to form a magnetic core, the circumferential direction of the magnetic core is the length direction of the ribbon. Therefore, annealing with a magnetic field applied along the circumferential direction of the wound magnetic core is a form of longitudinal magnetic field annealing.

The toroid-like magnetic core can have a ribbon curvature radius of 10 mm to 200 mm when loosened, and the _{ribbon relaxation rate defined by (2-R w} / R _f ) is greater than 0.93. Will be big. Here, R _w and R _f are the radius of curvature of the ribbon before the ribbon is released and the radius of curvature of the ribbon after the ribbon is released in the unconstrained state, respectively.

[0015] The toroidic magnetic core can have _Br / B _{800 greater than 0.7, where Br} and B ₈₀₀ have applied magnetic fields of 0 A / m and 800 A / m (in residual magnetism), respectively. It is the magnetic induction at the time of.

[0016] The toroid-like magnetic core has a core loss in the range of 0.15 W / kg to 0.4 W / kg (including values from 0.16 W / kg to 0.31 W / kg) at 1.6 T and 50 Hz. , Each of the core losses in the range of 0.2 W / kg to 0.5 W / kg (including values from 0.26 W / kg to 0.38 W / kg) at 1.6 T and 60 Hz excitation can be shown. it can. The coercive force may be less than 4 A / m and may be less than 3 A / m. The coercive force may be in the range of 2 A / m to 4 A / m (including values in the range of 2.2 A / m to 3.7 A / m).

[0017] Toroid-like magnetic cores can be made into transformer cores, electric chokes, power inductors, and other similar types.
[0018] The toroid-like magnetic core has a core loss of 3 W / kg at 0.1 T magnetic induction, 10 W / kg core loss at 0.2 T magnetic induction, and 28 W / kg at 0.4 T magnetic induction at 10 kHz. It can have a core loss of kg.

[0019] Toroid-like magnetic cores can be made into transformer cores operated at high frequencies, power inductor cores, and others of that kind.
[0020] toroidal core can have a range of _{B 800} from 1.7T have close to the saturation induction _{B S} to 1.78T.

[0021] When the magnetic field applied along the length of the ribbon is zero, the toroidic magnetic core can be heat treated with the magnetic field applied along the width of the ribbon. This procedure is referred to in the present disclosure as transverse magnetic field annealing (orthogonal magnetic field annealing) because the width direction of the ribbon traverses the length direction of the ribbon. By using a magnetic field along the width direction of the ribbon, the BH characteristics of the toroid-like magnetic core can be modified. This procedure can be used to modify the effective magnetic permeability of a toroid-like magnetic core.

The toroid-like magnetic core according to the above paragraph can be used, for example, in a power inductor that carries a large current, or in a current transformer. Such current transformers can also be used in electricity meters.

で表される組成を有するナノ結晶質合金のリボンを含み、ここで０．６≦ｘ＜１．２、１０≦ｙ≦２０、０≦（ｙ＋ｚ）≦２４、および０≦ａ≦１０、０≦ｂ≦５であり、全ての数値は原子パーセントであり、そして残部はＦｅおよび付随的不純物であり、またＡはＮｉ、Ｍｎ、Ｃｏ、Ｖ、Ｃｒ、Ｔｉ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、ＴａおよびＷから選択される少なくとも一つの元素である任意の含有物であり、またＸはＲｅ、Ｙ、Ｚｎ、Ａｓ、Ｉｎ、Ｓｎおよび希土類元素から選択される少なくとも一つの元素である任意の含有物であり、ナノ結晶質合金のリボンは、４０ｎｍ未満の平均の粒子サイズのナノ結晶が非晶質のマトリックスの中に分散していて、そしてこのナノ結晶がリボンの３０容積パーセントよりも多くを占めているような局所的構造を有する。組成は、本開示において論じられる組成のうちのいずれであってもよい。 [0023] In the first aspect of the present invention, the magnetic core is

Includes a ribbon of nanocrystalline alloy having the composition represented by, where 0.6 ≦ x <1.2, 10 ≦ y ≦ 20, 0 ≦ (y + z) ≦ 24, and 0 ≦ a ≦ 10, 0. ≤b ≤ 5, all numbers are atomic percentages, and the balance is Fe and incidental impurities, and A is Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Any inclusion that is at least one element selected from Ta and W, and X is any inclusion that is at least one element selected from Re, Y, Zn, As, In, Sn and rare earth elements. The material, nanocrystalline alloy ribbons, have nanocrystals with an average particle size of less than 40 nm dispersed in an amorphous matrix, and these nanocrystals make up more than 30 volume percent of the ribbon. It has a local structure that seems to occupy. The composition may be any of the compositions discussed in this disclosure.

[0024] In a second aspect of the invention, in the magnetic core of the first aspect of the invention, the ribbon is at a temperature in the range of 430 ° C. to 550 ° C. at a heating rate of 10 ° C./sec or higher for less than 30 seconds. It has undergone heat treatment, tensions between 1 MPa and 500 MPa are applied during the heat treatment, and the ribbon is wound after the heat treatment to form a wound magnetic core.

[0025] In the third aspect of the present invention, in the magnetic core of the second aspect of the present invention, the magnetic core is applied at a magnetic field of less than 4 kA / m applied along the circumferential direction of the magnetic core, and has a temperature of 400 ° C. to 500 ° C. It is further heat-treated in a rolled form over 1.8 ks (kiloseconds) to 10.8 ks at temperatures up to.

[0026] In the fourth aspect of the present invention, in any of the first to third aspects of the present invention, the magnetic core is a wound magnetic core, and the round portion of the magnetic core has a radius of curvature when loosened. Consists of a ribbon with a radius between 10 mm and 200 mm, and the rounded portion of the magnetic core is one in which the ribbon relaxation rate defined by _{(2-R w} / R _{f) is greater than 0.93.} Here, R _w and R _f are the radius of curvature of the ribbon before the ribbon is released and the radius of curvature of the ribbon after the ribbon is released in the unconstrained state, respectively.

[0027] In a fifth aspect of the invention, in the magnetic core of any of the second to fourth aspects of the invention, the nanocrystalline alloy ribbon has an average heating rate greater than 10 ° C./sec. The heat treatment is performed from room temperature to a predetermined holding temperature of more than 430 ° C. and lower than 550 ° C., and the holding time is less than 30 seconds at this time.

[0028] In a sixth aspect of the invention, in any of the magnetic cores of any of the second to fourth aspects of the invention, the nanocrystalline alloy ribbon has an average heating rate greater than 10 ° C./sec. The heat treatment is performed from 300 ° C. to a predetermined holding temperature of more than 450 ° C. and less than 520 ° C., and the holding time is less than 30 seconds at this time.

[0029] In the seventh aspect of the present invention, in the magnetic core of the sixth aspect of the present invention, the holding time in the process of forming the magnetic core is less than 20 seconds.
[0030] The magnetic core according to the first to seventh aspects of the present invention can be used in an apparatus that is a power distribution transformer. The magnetic core according to the first to seventh aspects of the present invention can have a coercive force in the range of 2 A / m to 4 A / m. The magnetic cores of the first to seventh aspects of the present invention can be used in devices such as power distribution transformers or inductive magnetometers for power management operating in commercial and high frequencies. Their magnetometers have a coercive force in the range of 2A / m to 4A / m, a core loss of 0.2W / kg to 0.5W / kg at 60Hz and 1.6T, and 0 at 50Hz and 1.6T. It can have a core loss of .15 W / kg to 0.4 W / kg and also have a B _{800 greater than 1.7 T.} The magnetic cores of the first to seventh aspects of the present invention can be utilized in devices that are transformers used in induction magnetometers or power electronics for power management operating at commercial and high frequencies. Yes, their magnets have a core loss of less than 30 W / kg at operating induction levels of 10 kHz and 0.5 T, and a B ₈₀₀ of more than 1.7 T.

で表される組成を有し、ここで０．６≦ｘ＜１．２、１０≦ｙ≦２０、０≦（ｙ＋ｚ）≦２４、および０≦ａ≦１０、０≦ｂ≦５であり、全ての数値は原子パーセントであり、そして残部はＦｅおよび付随的不純物であり、またＡはＮｉ、Ｍｎ、Ｃｏ、Ｖ、Ｃｒ、Ｔｉ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、ＴａおよびＷから選択される少なくとも一つの元素である任意の含有物であり、またＸはＲｅ、Ｙ、Ｚｎ、Ａｓ、Ｉｎ、Ｓｎおよび希土類元素から選択される少なくとも一つの元素である任意の含有物であり、そして熱処理の後にリボンを巻いて、それにより巻き磁心を形成する。 [0031] In a further aspect of the invention, the method of making a magnetic core includes: heating an amorphous alloy ribbon at a temperature in the range of 430 ° C. to 550 ° C. at a heating rate of 10 ° C./sec or higher. Heat treatment was performed for less than 30 seconds, and during this heat treatment, tension between 1 MPa and 500 MPa was applied, and the ribbon was

It has a composition represented by, where 0.6 ≦ x <1.2, 10 ≦ y ≦ 20, 0 ≦ (y + z) ≦ 24, and 0 ≦ a ≦ 10, 0 ≦ b ≦ 5. All numbers are atomic percentages, and the balance is Fe and incidental impurities, and A is selected from Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta and W. Any inclusion that is at least one element, and X is any inclusion that is at least one element selected from Re, Y, Zn, As, In, Sn and rare earth elements, and for heat treatment. Later, the ribbon is wound, thereby forming a wound core.

[0032] In a further aspect of the invention, the magnetic core is composed of 0.6 to 1.2 atomic percent of Cu, 10 to 20 atomic percent of B, and more than 0 atomic percent to 10 atomic percent. Includes a nanocrystalline alloy ribbon having a composition of an iron-based alloy containing Si (B and Si have a combined content of 10 to 24 atomic percent), and the nanocrystalline alloy ribbon is less than 40 nm. Nanocrystals of average particle size are dispersed in an amorphous matrix, and have a local structure such that the nanocrystals occupy more than 30 volume percent of the ribbon. The magnetic core comprises one or more of the features described above (including magnetic properties) for the first to seventh aspects discussed above or those described elsewhere in the present disclosure. It may be satisfied.

で表される合金組成を有し、ここで０．６≦ｘ＜１．２、１０≦ｙ≦２０、０＜ｚ≦１０、１０≦（ｙ＋ｚ）≦２４、０≦ａ≦１０、０≦ｂ≦５、そして残部はＦｅおよび付随的不純物であり、またＡはＮｉ、Ｍｎ、Ｃｏ、Ｖ、Ｃｒ、Ｔｉ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、Ｔａ、Ｗ、Ｐ、Ｃ、ＡｕおよびＡｇから選択される少なくとも一つの元素である任意の含有物であり、またＸはＲｅ、Ｙ、Ｚｎ、Ａｓ、Ｉｎ、Ｓｎおよび希土類元素から選択される少なくとも一つの元素である任意の含有物であり、全ての数値は原子パーセントであり、またこのリボンは非晶質のマトリックスの中に分散している４０ｎｍ未満の平均の粒子サイズのナノ結晶を有する局所的構造を有し、ナノ結晶はリボンの３０容積パーセントよりも多くを占めていて、そしてリボンは少なくとも２００ｍｍのリボン曲率半径を有する。磁心は、上で論じた第１から第７までの態様について上で説明した（磁気特性を含めた）特徴あるいは本開示の他の部分で説明する特徴のうちの一つ以上を含むか、あるいは満たしていてもよい。 [0033] In a further aspect of the invention, the nanocrystalline alloy ribbon

It has an alloy composition represented by, where 0.6 ≦ x <1.2, 10 ≦ y ≦ 20, 0 <z ≦ 10, 10 ≦ (y + z) ≦ 24, 0 ≦ a ≦ 10, 0 ≦ b ≦ 5, and the balance is Fe and ancillary impurities, and A is from Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta, W, P, C, Au and Ag. Any inclusion that is at least one element of choice, and X is any inclusion that is at least one element selected from Re, Y, Zn, As, In, Sn and rare earth elements. All numbers are atomic percent, and the ribbon has a local structure with nanocrystals of average particle size less than 40 nm dispersed in an amorphous matrix, the nanocrystals being 30 of the ribbon. It occupies more than a percentage of volume, and the ribbon has a ribbon radius of curvature of at least 200 mm. The magnetic core comprises one or more of the features described above (including magnetic properties) for the first to seventh aspects discussed above or those described elsewhere in the present disclosure. It may be satisfied.

[0034] By discussing the following detailed description of embodiments and accompanying drawings, the present invention will be better understood and further advantages will become apparent.
[0035] FIG. 1 illustrates the BH behavior of the heat-treated ribbon according to the aspect of the present invention, where H is the applied magnetic field and B is the generated magnetic induction. [0036] FIGS. 2A, 2B and 2C show the magnetic domain structures observed for the flat surface (FIG. 2A), recessed surface (FIG. 2B) and convex surface (FIG. 2C) of the heat treated ribbon of the embodiment of the present invention. Is shown. As indicated by the white and black arrows, the directions of magnetization in the two magnetic domains indicated by black and white are 180 ° different from each other. [0037] FIG. 3 shows detailed magnetic domain patterns at points 1, 2, 3, 4, 5 and 6 shown in FIG. 2C. [0038] Figures 4A and 4B show the upper half of the BH behavior obtained for a sample with the composition _{of Fe 81} Cu ₁ Mo _0.2 Si ₄ B _{13.8, which was first tensioned at 3 MPa.} Annealing at a heating rate of 50 ° C./s for 8 seconds in a heating bath at 481 ° C. (shown by curve B (dotted line)), then at 430 ° C. for 5400 seconds using a magnetic field of 1.5 kA / m. It is the one obtained by secondary annealing (shown by curve A). The curves in FIG. 4A on the left and FIG. 4B on the right are data obtained at magnetic fields up to 80 A / m and magnetic fields up to 800 A / m, respectively. _{B 80,} which is a magnetic induction in a magnetic field of _{80 A / m, and B 800,} which is a magnetic induction in a magnetic field of 800 A / m, are also shown. These quantities are used to characterize the magnetic properties of the alloy according to aspects of the invention. _{[0039] FIGS. 5A and 5B are from Fe 81} Cu ₁ Mo _0.2 Si ₄ B _13.8 alloy having a core size of (OD, ID) = (96.0, 90.0) listed in Table 2. shows the upper half of the BH behavior of toroidal magnetic core was produced (FIG. 5A), also showing the core loss P (W / kg) as a function of the operating magnetic flux _{B m} at frequency of 10kHz in Figure 5B. [0040] FIGS. 6A and 6B show the core loss at 60 Hz shown by curve A and the core loss at 50 Hz shown by curve B as a function _{of the excitation flux density B m in FIG. 6A and the BH loop in FIG. 6B.} The iron core has dimensions of OD = 153 mm, ID = 117 mm and H = 25.4 mm and is wound from a ribbon having a chemical composition of _{Fe 81.8} Cu _0.8 Mo _0.2 B _13. FIG. 7 shows a typical P-type alloy (indicated by P) and a typical Q-type alloy (indicated by Q) according to aspects of the invention and conventional 6.5% Si steel (denoted by Q). A), Fe-based amorphous alloy (B), and nanocrystalline Finemet FT3 alloy (C) were compared with _{core loss P (W / kg) vs. working magnetic induction B m (T) at a frequency of 10 kHz.} ing. [0042] FIGS. 8A and 8B show an example of an elliptical magnetic core according to an aspect of the present invention (shown by 71) and a DC BH loop obtained for this magnetic core (shown by 72). [0043] FIG. 9 shows the iron core loss P (W / kg) as a function of the operating magnetic flux density Bm (T) of the magnetic core at frequencies of 400 Hz, 1 kHz, 5 kHz and 10 kHz, and is measured for the magnetic core of FIG. 8A. is there. [0044] FIG. 10 shows the magnetic permeability vs. operating frequency for the magnetic core of FIGS. 8A-B. [0045] FIG. 11A shows the profile of the annealing temperature that characterizes the rapid temperature rise of the magnetic core in aspects of the present invention, tested for cooling of the magnetic core from room temperature to 500 ° C. and subsequent cooling. [0046] FIG. 11B shows the BH of the magnetic core of FIG. 11A undergoing further heat treatment as secondary annealing at 430 ° C. for 5.4 ks using a magnetic field of 3.5 kA / m applied along the circumferential direction of the magnetic core. Shows behavior.

The ductile metal ribbon used in aspects of the present invention can be cast by the rapid solidification method described in US Pat. No. 4,142,571. The shape of the ribbon is suitable for heat treatment after the ribbon is manufactured, and this heat treatment is used to control the magnetic properties of the cast ribbon.

[0048] This composition of the ribbon used in aspects of the present invention comprises 0.6 to 1.2 atomic percent Cu, 10 to 20 atomic percent B, and 10 atomic percent greater than 0 atomic percent. The composition of the iron-based alloy may contain up to an amount of Si (the combined content of B and Si is in the range of 10 to 24 atomic percent). The alloy also contains 0.01 at least one element selected from the group Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta, W, P, C, Au and Ag. It may be included in an amount of up to 10 atomic percent (this range includes values in the range 0.01-3 atomic% and 0.01-1.5 atomic%). When Ni is included in the composition, Ni may be in the range of 0.1-2 or 0.5-1 atomic percent. When Co is included, Co may be contained in the range of 0.1 to 2 or 0.5 to 1 atomic percent. When elements selected from the group Ti, Zr, Nb, Mo, Hf, Ta and W are included, the total content of these elements is less than 0.4 atomic percent in total (0.3 for this). It may be any value (including any value less than or less than 0.2). The alloy may also contain at least one element selected from the group of Re, Y, Zn, As, In, Sn, and rare earth elements in an amount of any value less than or equal to 5 atomic percent (5 atomic percent or less). This includes values below and below 2, 1.5 and 1 atomic percent).

[0049] The aforementioned range for at least one element selected from the group Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta, W, P, C, Au and Ag ( Each of the individual predetermined ranges for Co and Ni) described above for at least one element selected from the group of Re, Y, Zn, As, In, Sn, and rare earth elements. It may coexist with each of the predetermined ranges. In any of the compositional variations, including those discussed above, Fe and all incidental or unavoidable impurities are the remaining constituents or substantial to make up the total atomic percent of 100. Can be a component. In any of the above compositional configurations, the element P can be excluded from the alloy composition. All compositional configurations can be carried out provided that the Fe content is at least 75, 77 or 78 atomic percent.

[0050] Examples of one composition range suitable for aspects of the present invention are 80-82 atomic% Fe, 0.8-1.1 atomic% or 0.9-1.1 atomic% Cu, 3-. Select from the group of 5 atomic% Si, 12-15 atomic% B, and Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta, W, P, C, Au and Ag. The total of those composed of one or more elements to be formed is 0 to 0.5 atomic%, and the above-mentioned atomic percentage is 100 atomic% in total, apart from incidental or unavoidable impurities. Be selected.

[0051] The composition of the alloy may consist solely of, or essentially consist of, a range of elements and ancillary impurities specifically listed in the previous two paragraphs. The composition of the alloy may also consist, or essentially consist, of the above-mentioned predetermined ranges (for these particular elements) of the elements Fe, Cu, B, and Si, as well as incidental impurities. The presence of any incidental impurities, including practically unavoidable impurities, is not excluded by any composition claimed herein. Selective components (Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta, W, P, C, Au, Ag, Re, Y, Zn, As, In, Sn, and rare earth elements. ), They can be present in an amount of at least 0.01 atomic%.

[0052] In an embodiment of the present invention, the chemical composition of the ribbon _is can be represented by _{Fe 100-x-y-z} Cu x B y Si z, where, 0.6 ≦ x <1.2,10 ≦ y ≦ 20 and 10 ≦ (y + z) ≦ 24, and these numerical values are atomic percentages. These alloys according to aspects of the present invention are referred to as Q-type alloys in this application.

A Cu content of 0.6 ≤ x <1.2 is used because when x ≥ 1.2, the clusters formed by the Cu atoms are for fine crystalline particles of bccFe. This is because it serves as a seed. The size of such clusters affected the magnetic properties of the heat-treated ribbon, but its size was difficult to control. Therefore, x is set to be less than 1.2 atomic percent. Since a specific amount of Cu was required to induce nanocrystallization on the ribbon by heat treatment, it was determined that Cu ≥ 0.6.

[0054] Due to the positive heat of mixing in the amorphous Fe-B-Si matrix, Cu atoms tend to be dense and reduce the boundary energy between the matrix and the Cu cluster phase. It was. In alloys of related technical fields, elements such as P and Nb have been added to control the diffusion of Cu atoms in the alloy. Since these elements reduced the saturated magnetic induction in the heat treated ribbon, they may be eliminated or minimized in the alloy in aspects of the invention. Alloys in the relevant technical field having these elements are classified as P-type alloys in the present disclosure. Thus, either or both of the elements P and Nb may not be present in the alloy, or may be absent except in accidental or unavoidable amounts. Alternatively, instead of the absence of P, P may be included in the minimum amount discussed herein.

[0055] Instead of controlling the diffusion of Cu by adding P or Nb to the alloy as described above, the rapid heating of the ribbon does not give sufficient time for the Cu atoms to diffuse. The process of heat treatment is modified in a straightforward manner.

[0056] previously presented _{Fe 100-x-y-z} Cu x B y Si z (0.6 ≦ x <1.2,10 ≦ y ≦ 20,0 <z ≦ 10,10 ≦ (y + z) ≦ In the composition 24), in order to achieve saturated magnetic induction greater than 1.7T in the heat treated alloy containing nanocrystals of bcc-Fe, the Fe content (if such saturated magnetic induction is desirable) is , 75 atomic percent, preferably 77 atomic percent, more preferably more than 78 atomic percent, or at least these values. Ancillary impurities commonly found in Fe raw materials were acceptable as long as the Fe content was sufficient to achieve saturated magnetic induction above 1.7 T. These amounts of Fe greater than 75, 77 or 78 atomic percent include Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta, W, P, C, Au, discussed below. And Ag inclusions, and independent of the inclusions of Re, Y, Zn, As, In, Sn, and rare earth elements, can be carried out in any composition of the present disclosure.

[0057] previously presented _{Fe 100-x-y-z} Cu x B y Si z (0.6 ≦ x <1.2,10 ≦ y ≦ 20,0 <z ≦ 10,10 ≦ (y + z) ≦ In the composition 24), the Fe _{content represented by Fe 100-x-yz} is from 0.01 atomic percent to 10 atomic percent, preferably from 0.01 to 3 atomic percent, most preferably 0.01. Up to 1.5 atomic percent at least one selected from the group Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta, W, P, C, Au, and Ag. It may be replaced with. Elements such as Ni, Mn, Co, V and Cr tend to alloy in the amorphous phase of the heat treated ribbon, resulting in Fe-rich nanocrystals with fine particle size and thus saturation. Increases magnetic induction and improves the soft magnetism of the heat treated ribbon. The presence of these elements (including the range of individual elements discussed below) may be present in combination with a total Fe content that is greater than 75, 77 or 78 atomic percent.

[0058] Of the above-mentioned Fe substitution elements Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta, W, P, C, Au, and Ag, Co and Ni The addition increased the Cu content, resulting in fine nanocrystals in the heat-treated ribbon, which in turn improved the soft magnetism of the ribbon. In the case of Ni, its content was preferably from 0.1 atomic percent to 2 atomic percent, more preferably 0.5 to 1 atomic percent. When the Ni content was less than 0.1 atomic percent, the processing suitability of the ribbon was inferior. When the Ni content exceeded 2 atomic percent, the saturated magnetic induction and coercive force in the ribbon decreased. In the case of the addition of Co, the Co content was preferably between 0.1 and 2 atomic percent, more preferably between 0.5 and 1 atomic percent.

[0059] Further, among the above-mentioned Fe substitution elements Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta, W, P, C, Au, and Ag, Ti, Elements such as Zr, Nb, Mo, Hf, Ta and W tend to alloy in the amorphous phase of the heat-treated ribbon, contributing to the stability of the amorphous phase and the softness of the heat-treated ribbon. Improved magnetism. However, the atomic size of these elements is larger than that of other transition metals such as Fe, and when their content is high, the soft magnetism of the heat-treated ribbon is reduced. Therefore, the content of these elements was preferably less than 0.4 atomic percent. Their total content was preferably less than 0.3 atomic percent, or more preferably less than 0.2 atomic percent.

[0060] previously presented _{Fe 100-x-y-z} Cu x B y Si z (0.6 ≦ x <1.2,10 ≦ y ≦ 20,0 <z ≦ 10,10 ≦ (y + z) ≦ In the composition 24), _{less than 5 atomic percent, more preferably less than 2 atomic percent of Fe, as indicated by Fe 100-x-yz} , comes from the group of Re, Y, Zn, As, In, Sn, and rare earth elements. It may be replaced with one of. When high saturated magnetic induction was desired, the content of these elements was preferably less than 1.5 atomic percent, more preferably less than 1.0 atomic percent.

[0061] The ribbon of the composition described above can be subjected to the first heat treatment described below. The ribbon is heated to a predetermined holding temperature at a heating rate of over 10 ° C./sec. When the holding temperature is close to 300 ° C, the heating rate should generally exceed 10 ° C / sec. This is because it significantly affects the magnetic properties of the heat treated ribbon. Holding temperature is preferably greater than _(T x2 -50) ℃, _{where, T x2} is the temperature at which particles of crystalline precipitated. The holding temperature is preferably higher than 430 ° C. The temperature T _{x 2} can be determined by a commercially available differential scanning calorimetry (DSC). When heated, the alloy of the embodiment of the present invention crystallizes in two steps with two characteristic temperatures. At the higher characteristic temperature, the secondary crystal phase begins to precipitate, and this temperature is referred to as _{Tx2 in the present disclosure.} When the holding temperature was lower than 430 ° C., the precipitation followed by the growth of fine crystal particles was not sufficient. However, the highest holding temperature is lower than 530 ° C., which corresponds to _{T x 2 of the alloy of the embodiment of the present invention.} The holding time was preferably less than 30 seconds, more preferably less than 20 seconds, and most preferably less than 10 seconds. Some examples of the above process are presented in Examples 1 and 2.

The heat-treated ribbon in the above paragraph was rolled into a magnetic core, which was then heat treated between 400 ° C and 500 ° C for 900 seconds and 10.8 ks. The heat treatment time was preferably longer than 900 seconds, more preferably longer than 1.8 ks so that the stress was sufficiently relieved. If higher productivity was desired, the heat treatment time was less than 10.8 ks, preferably less than 5.4 ks. This additional process was found to homogenize the magnetic properties of the heat treated ribbon. Example 3 shows some of the results (FIG. 4) obtained by the process described above.

[0063] In the process of heat treatment, a magnetic field was applied to induce magnetic anisotropy in the ribbon. The applied magnetic field was high enough to magnetically saturate the ribbon, but it was preferably higher than 0.8 kA / m. The applied magnetic field was either in the form of DC (direct current), AC (alternating current) or pulse. The direction of the magnetic field applied during the heat treatment was predetermined depending on the need for a square, circular or linear BH loop. When the applied magnetic field was zero, BH behavior with a moderate square ratio of 50% to 70% occurred. Magnetic anisotropy is an important factor in controlling magnetic performance such as magnetic loss in magnetic materials, and it is easy to control magnetic anisotropy by heat treatment of the alloy of the embodiment of the present invention. It was advantageous.

[0064] Mechanical tension was applied instead of the magnetic field applied during the heat treatment. This resulted in tension-induced magnetic anisotropy in the heat-treated ribbon. The effective tension was greater than 1 MPa and less than 500 MPa. An example of a BH loop obtained for a ribbon heat treated under tension is shown in FIG. The observed local magnetic domains are shown in FIGS. 2A-2C and 3.

Example 1
[0065] A rapidly solidified ribbon having a composition of _{Fe 81} Cu _1.0 Si ₄ B ₁₄ is placed on a 30 cm long bronze plate heated to 490 ° C. while applying a tension of 25 MPa to the ribbon from 3 to 15 Moved over seconds. It took 5 to 6 seconds for the ribbon to reach the bronze plate temperature of 490 ° C., and the heating rate was 50 to 100 ° C./sec. The heat-treated ribbon was characterized with a commercially available BH loop tracer, and the results are shown in FIG. Here, the thin solid line corresponds to the BH loop for the as-cast ribbon or the as-quenched ribbon (As-Q), while the solid, dotted and half-dotted lines are 4.5 m / min and 3 m / min, respectively. , And corresponds to a BH loop for a ribbon that has been tension annealed using a rate of 1.5 m / min.

[0066] Figures 2A, 2B and 2C show the magnetic domains observed by the Kerr microscope for the ribbon of Example 1. 2A, 2B and 2C are from the flat, convex and recessed surfaces of the ribbon, respectively. As shown there, the direction of magnetization indicated by the white arrow in the black portion is 180 ° different from the direction of magnetization in the white portion indicated by the black arrow. 2A and 2B show that the magnetic properties are uniform over the width of the ribbon and along the length direction. On the other hand, in the compressed portion corresponding to FIG. 2C, the local stress changes from point to point.

[0067] FIG. 3 shows detailed magnetic domain patterns at points 1, 2, 3, 4, 5 and 6 of the ribbon in FIG. 2C. These domain patterns indicate the direction of magnetization near the surface of the ribbon, which reflects the local stress distribution in the ribbon.

Example 2
Although the heat treated ribbon was relatively flat, a radius of curvature was created in the ribbon during the initial heat treatment of the ribbon according to aspects of the invention. To determine the range of radius of curvature R (mm) of the _ribbon, in the heat-treated ribbon is greater than _{B 80} / _{B 800 0.90,} was examined _{B 80} / _{B 800} ratio as a function of the radius of curvature of the ribbon , Its radius of curvature was altered by wrapping a heat-treated ribbon over a round surface with a known radius of curvature. The results are shown in Table 1. The data in Table 1 are _{summarized as B 80} / B ₈₀₀ = 0.0028R + 0.48. The data in Table 1 are used to design the magnetic core, for example, to design the magnetic core manufactured from the laminated ribbon.

[0069] Sample 1 corresponds to the case of the flat ribbon of FIG. 2A in Example 1, where the magnetization distribution is relatively uniform but has a large value of B ₈₀ / B ₈₀₀ , which is preferable. .. The amounts of B ₈₀ , B ₈₀₀ and _BS (saturated magnetic induction) are determined in FIGS. 4A and 4B. Figure 4A, as shown in _{4B, B 800} is similar to the _{B S} (saturation induction), the BH loop material of a square of the present invention, as well as in practical _{applications, B 800} is treated as _{B S.} In FIGS. 4A and 4B, the residual magnetic induction _Br is determined by the induction at H = 0.

Example 3
[0070] Fe ₈₁ Cu ₁ Mo _0.2 Si ₄ B _13.8 alloy ribbon strip samples (elongated samples) were first used in a heating bath at 470 ° C. at a heating rate greater than 50 ° C./sec. Annealed on a hot plate for 15 seconds, then secondary annealed at 430 ° C. for 5400 seconds in a magnetic field of 1.5 kA / m. Another sample of strips of the same chemical composition was first annealed in a heating bath at 481 ° C. using a heating rate greater than 50 ° C./sec for 8 seconds with a tension of 3 MPa, then 1.5 kA / sec. Secondary annealing was performed at 430 ° C. for 5400 seconds in a magnetic field of m. Examples of BH loops obtained for these strips before and after secondary annealing are shown in FIGS. 4A and 4B. The solid line A shows after the secondary annealing, and the broken line shows after the first annealing. The amount of B ₈₀ (magnetic induction at 80 A / m magnetic field excitation) and the amount of B ₈₀₀ (magnetic induction at 800 A / m) are also shown. These amounts are used to characterize the heat treated material of the present invention. As shown, the coercive force represented by both lines is 3.8 A / m, which is less than 4 A / m. Each _{B r,} the value of _{B 80,} and _{B 800} for the curve A, 1.33T, 1.65T, and is 1.67T. _B r of the curve _{B, B 80,} and each value of _{B 800,} is 0.78T, 1.49T, and 1.63T.

Example 4
[0071] direct contact with the ribbon ribbon having a composition of the above-mentioned _{Fe 100-x-y-z} Cu x B y Si z, the first brass or Ni plated copper surface having a radius of curvature of 37.5mm Heat treatment at temperatures between 470 ° C and 530 ° C, followed by rapid heating of the ribbon above 300 ° C at a heating rate greater than 10 ° C / sec with a contact time between 0.5 and 20 seconds. did. The resulting ribbon had a radius of curvature between 40 mm and 500 mm. Then, the heat-treated ribbon was wound to form a toroid-like magnetic core, which was heat-treated at 400 ° C. to 500 ° C. for 1.8 ks to 5.4 ks (kiloseconds).

The toroid-like magnetic core according to the previous paragraph has a ribbon curvature radius in the range of 10 mm to 200 mm when loosened, and the ribbon relaxation rate defined by _{(2-R w} / R _{f) is 0.} It was rolled to be larger than 93. Here, R _w and R _f are the radius of curvature of the ribbon before the ribbon is released and the radius of curvature of the ribbon after the ribbon is released in the unconstrained state, respectively.

[0073] A toroid-like magnetic core having an outer diameter (OD) = 42.0 mm to 130.5 mm, an inner diameter (ID) = 40.0 mm to 133.0 mm, and a height (H) = 25.4 mm to 50.8 mm. , Manufactured from annealed ribbon with a BH loop generally characterized by FIG. 5A. The height H of the magnetic core was 25.4 mm for the alloys A, B and C and 50.8 mm for the alloy D. The chemical compositions of the alloys A, B, C and D listed in Table 2 are Fe ₈₁ Cu ₁ Mo _0.2 Si ₄ B _13.8 , Fe ₈₁ Cu ₁ Si ₄ B ₁₄ and Fe _81.8 Cu _{0, respectively. 8} Mo _0.2 Si _4.2 B ₁₃ and Fe ₈₁ Cu ₁ Nb _0.2 Si ₄ B _13.8 . Magnetic properties such as core loss and excitation power of the toroid-like magnetic core were characterized by test methods according to the ASTMA927 standard. An example of iron core loss as a function of the excitation magnetic flux density Bm obtained for a ribbon-based magnetic core of Fe ₈₁ Cu ₁ Mo _0.2 Si ₄ B _{13.8 is shown in FIG. 5B.} Other relevant characteristics, such as B _{800, B r} and _{H C} was determined by measuring the BH loop for the sample of the magnetic core.
Table 2 shows some examples of these properties.

[0074] FIGS. 6A and 6B are first annealed at 499 ° C. for 1 second with a ribbon tension of 5 MPa, and then 5 at 430 ° C. with a magnetic field of 2.2 kA / m along the circumferential direction of the magnetic core. Magnetic properties obtained from a magnetic core with dimensions of OD = 153 mm, ID = 117 mm and H = 25.4 mm using an alloy having the composition D shown in Table 2 produced by secondary annealing over .4 ks. An example of the graph is shown.

Table 2 . Physical and magnetic properties of the toroid-like magnetic core of aspects of the present invention. Each _{P 16/60} and _{P 16/50} are core loss in the excitation of 1.6T and 60Hz and 50 _Hz;; alloy A, the B and _C H = 25.4mm; _t C = ribbons contact time _{B r} is 800A Remanent magnetism at / m, B ₈₀₀ is magnetic induction.

[0075] In Table 2, when the alloy of the embodiment of the present invention is heat-treated, the saturated magnetic induction in the range of 1.70 T to 1.78 T and the coercive force in the range of 2.2 A / m to 3.7 A / m are shown. it has been shown to have an H _C. These should be compared with the _B S = 2.0 T and _H C = 8A / m for a 3% silicon steel magnetic core that the alloy of the embodiment of the present invention based conventional silicon steel in the operation of 50Hz and 60Hz It shows that the iron core loss is about 1/2 of the value of. The data in Table 2 give core losses of 0.16 W / kg to 0.31 W / kg and 0.26 W / kg to 0.38 W / kg, respectively, at 50 Hz / 1.6 T and 60 Hz / 1.6 T. Core loss in the 50Hz and 60Hz in the different levels of magnetic induction is shown in FIG. 6A, and FIG. 6B shows that low excitation power by a low coercivity _(H C <4A / m) narrow BH loop with the results. This excitation power is the minimum energy for exciting the magnetic core. Therefore, these magnetic cores are suitable for magnetic cores used in power transformers and induction magnetometers that transmit large currents.

Example 5
[0076] The high frequency magnetic properties of the toroid-like magnetic core of Example 4 were evaluated according to the ASTM A927 standard. _{An example of the iron core loss P (W / kg) vs. the operating magnetic flux B m} (T) for the toroid-like magnetic cores of OD = 96.0 mm, ID = 90.0 mm and H = 25.4 mm from Table 2 is shown in FIG. 5B. Shown. Similar data obtained for another alloy of aspects of the invention shown by line Q, 6.5% Si steel (line A), amorphous Fe-based alloy (line B), nanocrystalline Finement FT3. Comparison is made in FIG. 7 with data on alloys (line C) and P-type alloys (line P) in related technical fields. Since the FT3 alloy has a saturated magnetic induction of 1.2T, which is much lower than the value of this alloy (1.7T to 1.78T), the alloys of the embodiments of the present invention operate at much higher operating magnetic induction. It can be made so that small magnetic parts can be constructed. FIG. 7 also shows that for operating magnetic induction levels above 0.2 T at high frequencies, the core loss in the alloy-based magnetic cores of the present invention is lower than in prior art P-type alloys. For example, FIG. 7 shows that the core loss of the magnetic core of the embodiment of the present invention at 10 kHz and 0.5 T magnetic induction is 30 W / kg, which is 40 W for a prior art P-type alloy excited under the same conditions. It shows that it is comparable to / kg. Therefore, the magnetic core of the embodiment of the present invention is suitable for use as an inductor for power management used in power electronics.

Example 6
The quenched ribbon was heat treated according to the first heat treatment process described above. Then, the heat-treated ribbon was wound to form an elliptical magnetic core as shown in FIG. 8A. Here, the straight portion of the magnetic core has a length of 58 mm, the curved portion has a radius of curvature of 29 × 2 mm, and the inside and outside of the magnetic core have magnetic path lengths of 317 mm and 307 mm, respectively. It was. The wound magnetic core was then heat treated by the secondary annealing process previously described in the first paragraph of "Example 4". Next, a DCBH loop was obtained for the secondary annealed magnetic core as in Example 1. This is shown by the curve 72 in FIG. 8B. The iron core loss was then measured according to the ASTM A927 standard and the results are shown in FIG. 9 as a function of the magnetic flux density Bm (T) of the magnetic core at operating excitation frequencies of 400 Hz, 1 kHz, 5 kHz and 10 kHz. Permeability was measured as a function of frequency using an excitation magnetic field of 0.05T, which is shown in FIG. The core loss at 10 kHz and 0.2 T magnetic induction is 7 W / kg, which is considered to be comparable to the corresponding core loss of 10 W / kg measured using the toroid-wound magnetic core shown in FIG. 5B. Therefore, the magnetic performance at high frequencies is not significantly affected by the shape and size of the magnetic core, which means that the stress introduced during the manufacture of the magnetic core is sufficiently released by the secondary annealing of the embodiments of the present invention. It shows that it will be done.

Example 7
[0078] _{A ribbon having a chemical composition of Fe 81.8} Cu _0.8 Mo _0.2 Si _4.2 B ₁₃ and a width of 25.4 mm, as shown by the heating profile of FIG. 11A, at a tension of 5 MPa. Under 1 second, it was rapidly heated to 500 ° C. and air cooled. Next, the heat-treated ribbon was wound to obtain a magnetic core having a magnetic core height of OD = 96 mm, ID = 90 mm and 25.4 mm. Next, the wound magnetic core was heat-treated at 430 ° C. for 5.4 ks while applying a magnetic field of 3.5 kA / m along the circumferential direction of the magnetic core. When cooled to room temperature, the BH behavior of the magnetic core was measured by a commercially available BH hysteresis diagram device as in Example 1. The results are shown in FIG. 11B. This gives a square ratio of 0.96 and a coercive force of 3.4 A / m. Therefore, this magnetic core is suitable for applications operated in high magnetic induction.

Example 8
[0079] As shown in Table 3 below, 180 ° bend ductility tests were performed on the alloys of aspects of the present invention and the two alloys of '531 (as a comparative example). The 180 ° bend ductility test is commonly used to test whether a ribbon-shaped material breaks or cracks when bent 180 °. As shown herein, the product of aspects of the present invention did not show fracture in the bending test.

[0080] As used throughout this disclosure, the term "to" includes the end of the range. Thus, "from x to y" refers to the range including x and y and all of the midpoints between them, such midpoints are also part of the present disclosure. In addition, those skilled in the art will appreciate that numerical deviations of quantities are possible. Therefore, it should be understood that whenever reference is made to a numerical value in the specification or claims, additional values that are, or are such numerical values, fall within the scope of the invention.

[0081] Although some embodiments have been shown and described, those skilled in the art will recognize that changes can be made in these embodiments without departing from the principles and spirit of the present invention. The scope of the invention is defined in the claims and their equivalents.

Claims (31)

A magnetic core containing a ribbon of a nanocrystalline alloy having an iron-based alloy composition.
The composition of the iron-based alloy consists of Cu in an amount of 0.6 atomic percent or more and less than 1.2 atomic percent, B in an amount of 10 to 20 atomic percent, and Si in an amount of more than 0 atomic percent and up to 10 atomic percent. However, B and Si have a total content of 10 to 24 atomic percent and consist of ancillary impurities and iron, which is the remainder of the iron-based alloy composition of 100 atomic percent.
The nanocrystalline alloy ribbon contains nanocrystals with an average particle size of less than 40 nm dispersed in an amorphous matrix and contains more than 30 volume percent of the nanocrystalline alloy ribbon. Has a local structure that occupies
The magnetic core has a coercive force of less than 4 A / m.
The magnetic core.

A magnetic core containing a ribbon of a nanocrystalline alloy having a composition represented by, where 0.6 atomic% ≤ x <1.2 atomic%, 10 atomic% ≤ y ≤ 20 atomic%, 0 atomic% < z ≤ 10 atomic%, 10 atomic% ≤ (y + z) ≤ 24 atomic%, and 0 atomic% ≤ a ≤ 10 atomic%, 0 atomic% ≤ b ≤ 5 atomic%, atomic% is atomic%, and [Imperial] is the amount of ancillary impurities in atomic%, and A is at least one element selected from Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta and W. Is any inclusion that is, and X is any inclusion that is at least one element selected from Re, Y, Zn, As, In and rare earth elements, and Nb, Zr, Ta in the composition. And the total content of Hf is less than 0.3 atomic percent,
The nanocrystalline alloy ribbon contains nanocrystals with an average particle size of less than 40 nm dispersed in an amorphous matrix and contains more than 30 volume percent of the nanocrystalline alloy ribbon. Has a local structure that occupies
The magnetic core has a coercive force of less than 4 A / m.
The magnetic core. A magnetic core containing a ribbon of a nanocrystalline alloy having an iron-based alloy composition.
The composition of the iron-based alloy consists of Cu in an amount of 0.6 atomic percent or more and less than 1.2 atomic percent, B in an amount of 10 to 20 atomic percent, and Si in an amount of more than 0 atomic percent and up to 10 atomic percent. However, B and Si have a total content of 10 to 24 atomic percent and consist of ancillary impurities and iron, which is the remainder of the iron-based alloy composition of 100 atomic percent.
The nanocrystalline alloy ribbon contains nanocrystals with an average particle size of less than 40 nm dispersed in an amorphous matrix and contains more than 30 volume percent of the nanocrystalline alloy ribbon. Has a local structure that occupies
The magnetic core has a coercive force of less than 4 A / m and has a coercive force of less than 4 A / m.
The ribbon was heat-treated at a heating rate of 10 ° C./sec or higher for less than 30 seconds at a temperature in the range of more than 450 ° C. and up to 550 ° C. Is added, and the ribbon is rolled after heat treatment to form a rolled magnetic core,
core.

A magnetic core containing a ribbon of a nanocrystalline alloy having a composition represented by, where 0.6 atomic% ≤ x <1.2 atomic%, 10 atomic% ≤ y ≤ 20 atomic%, 0 atomic% < z ≤ 10 atomic%, 10 atomic% ≤ (y + z) ≤ 24 atomic%, and 0 atomic% ≤ a ≤ 10 atomic%, 0 atomic% ≤ b ≤ 5 atomic%, atomic% is atomic%, and [Imperial] is the amount of ancillary impurities in atomic%, and A is at least one element selected from Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta and W. And X is any inclusion that is at least one element selected from Re, Y, Zn, As, In, Sn and rare earth elements, and Nb, Zr in the composition. , Ta and Hf total content is less than 0.3 atomic percent
The nanocrystalline alloy ribbon contains nanocrystals with an average particle size of less than 40 nm dispersed in an amorphous matrix and contains more than 30 volume percent of the nanocrystalline alloy ribbon. Has a local structure that occupies
The magnetic core has a coercive force of less than 4 A / m and has a coercive force of less than 4 A / m.
The ribbon was heat-treated at a heating rate of 10 ° C./sec or higher for less than 30 seconds at a temperature in the range of more than 450 ° C. and up to 550 ° C. Is added, and the ribbon is rolled after heat treatment to form a rolled magnetic core,
core. The magnetic core is further heat-treated in a wound form for 1.8 ks (kiloseconds) to 10.8 ks at a temperature of 400 ° C. to 500 ° C. in a magnetic field of less than 4 kA / m applied along the circumferential direction of the magnetic core. The magnetic core according to claim 3 or 4. The magnetic core is a wound magnetic core, and the round portion of the magnetic core is composed of a ribbon having a radius of curvature between 10 mm and 200 mm when loosened, and the round portion of the magnetic core, (2-R _w. The ribbon relaxation rate defined by / R _f ) is greater than 0.93, where R _w and R _f are the first radius of curvature of the ribbon before the ribbon is released and the state in which the ribbon is wound, respectively. The magnetic core according to claim 1 or 2, which is the radius of curvature of the second ribbon when released from the magnetic core and is not constrained by the magnetic core. The nanocrystalline alloy ribbon is heat treated from room temperature to a predetermined holding temperature at an average heating rate greater than 10 ° C./sec, where the predetermined holding temperature exceeds 450 ° C. and is less than 550 ° C. The magnetic core according to claim 3 or 4 , wherein the holding time is less than 30 seconds. The nanocrystalline alloy ribbon is heat treated from 300 ° C. to a predetermined holding temperature at an average heating rate greater than 10 ° C./sec, at which time the predetermined holding temperature exceeds 450 ° C. and 520 ° C. The magnetic core according to claim 3 or 4, which is less than and has a holding time of less than 30 seconds. The magnetic core according to claim 8, wherein the holding time is less than 20 seconds. The magnetic core according to claim 1 or 2, wherein the composition of the ribbon of the nanocrystalline alloy contains at least 78 atomic% of Fe. The composition of the nanocrystalline alloy ribbon is at least selected from 0.01 atomic percent to 10 atomic percent Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta and W. The magnetic core according to claim 1 or 2, wherein one is included. The magnetic core according to claim 1, wherein the composition of the nanocrystalline alloy contains at least one selected from Nb, Zr, Ta and Hf in a total amount of less than 0.4 atomic percent. The magnetic core according to claim 1 or 2, wherein in the composition of the ribbon of the nanocrystalline alloy, the total amount of Re, Y, Zn, As, In and rare earth elements is less than 2.0 atomic percent. 13. The magnetic core according to claim 13, wherein the total amount of Re, Y, Zn, As, In and rare earth elements is less than 1.0 atomic percent. A transformer for power distribution including the magnetic core according to any one of claims 1 to 4. An inductive magnetometer for commercial and high frequency operating power management, comprising the magnetic core according to any one of claims 1 to 4. A transformer used in power electronics, which comprises the magnetic core according to any one of claims 1 to 4. An apparatus including the magnetic core according to any one of claims 1 to 4.
The magnetic core has a core loss of 0.2 W / kg to 0.5 W / kg at 60 Hz and 1.6 T and a core loss of 0.15 W / kg to 0.4 W / kg at 50 Hz and 1.6 T, and 1 The device having a B ₈₀₀ that exceeds .7 T, where the B ₈₀₀ is a magnetic induction when the applied magnetic field is 800 A / m. The magnetic core has an iron core loss of 30 W / kg or less at an operating induction level of 10 kHz and 0.5 T, and also has a B ₈₀₀ of more than 1.7 T, where the B ₈₀₀ is when the applied magnetic field is 800 A / m. The magnetic core according to any one of claims 1 to 4, which is the magnetic induction of the above. Has a _{B r} / _{B 800} and more than 1.7 T _{B 800} exceeds 0.8, where _{B r} and _{B 800} is a magnetic induction when the magnetic field was added each of 0A / m and 800A / m, The magnetic core according to any one of claims 1 to 4. It ’s a method of manufacturing a magnetic core.
The rapidly solidified alloy ribbon is heat treated at a heating rate of 10 ° C./sec or higher for less than 30 seconds at a temperature in the range of more than 450 ° C. to 550 ° C., and between 1 MPa and 500 MPa during this heat treatment. Applying tension and, after the heat treatment, winding a ribbon of heat-treated nanocrystalline alloy, thereby forming a wound magnetic core,
Including
The rapidly solidified alloy ribbon has an iron-based alloy composition.
The composition of the iron-based alloy consists of Cu in an amount of 0.6 atomic percent or more and less than 1.2 atomic percent, B in an amount of 10 to 20 atomic percent, and Si in an amount of more than 0 atomic percent and up to 10 atomic percent. However, B and Si have a total content of 10 to 24 atomic percent and consist of ancillary impurities and iron, which is the remainder of the iron-based alloy composition of 100 atomic percent.
The heat-treated nanocrystalline alloy ribbon contains nanocrystals with an average particle size of less than 40 nm dispersed in an amorphous matrix and is more than 30 volume percent of the nanocrystalline alloy ribbon. Has a local structure that occupies most of
The magnetic core has a coercive force of less than 4 A / m.
The method. It ’s a method of manufacturing a magnetic core.
The rapidly solidified alloy ribbon is heat treated at a heating rate of 10 ° C./sec or higher for less than 30 seconds at a temperature in the range of more than 450 ° C. to 550 ° C., and between 1 MPa and 500 MPa during this heat treatment. Applying tension and, after the heat treatment , winding a ribbon of heat-treated nanocrystalline alloy, thereby forming a wound magnetic core,
Including
The rapidly solidified alloy ribbon

It has the composition of an iron-based alloy represented by, where 0.6 atomic% ≤ x <1.2 atomic%, 10 atomic% ≤ y ≤ 20 atomic%, 0 atomic% <z ≤ 10 atomic%, 10 Atomic% ≤ (y + z) ≤24 atomic%, and 0 atomic% ≤a≤10 atomic%, 0 atomic% ≤b≤5 atomic%, atomic% is atomic%, and [impurity] is ancillary impurities. In atomic% of, and A is any inclusion that is at least one element selected from Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta and W. Yes, and X is any inclusion that is at least one element selected from Re, Y, Zn, As, In, Sn and rare earth elements, and the entire Nb, Zr, Ta and Hf in the composition. The content is less than 0.3 atomic percent
The heat-treated nanocrystalline alloy ribbon contains nanocrystals with an average particle size of less than 40 nm dispersed in an amorphous matrix and is more than 30 volume percent of the nanocrystalline alloy ribbon. Has a local structure that occupies most of
The magnetic core has a coercive force of less than 4 A / m.
The method. After winding the ribbon of the nanocrystalline alloy, it was wound for 1.8 ks to 10.8 ks at a temperature of 400 ° C. to 500 ° C. in a magnetic field of less than 4 kA / m applied along the circumferential direction of the magnetic core. 21 or 22. The method of claim 21 or 22, further comprising further heat treating the magnetic core in form. The pre-winding heat treatment is performed at an average heating rate greater than 10 ° C./sec, from room temperature to a predetermined holding temperature above 450 ° C. and below 550 ° C., with a holding time of less than 30 seconds. Item 21 or 22. It ’s a method of manufacturing a magnetic core.
Heat-treating a rapidly solidified alloy ribbon at a heating rate of 10 ° C./sec or higher for less than 30 seconds at a temperature in the range of 430 ° C. to 550 ° C., and tension between 1 MPa and 500 MPa during this heat treatment. In addition, the rapidly solidified alloy ribbon

It has a composition represented by, where 0.6 atomic% ≤ x <1.2 atomic%, 10 atomic% ≤ y ≤ 20 atomic%, 0 atomic% <z ≤ 10 atomic%, 10 atomic% ≤ ( y + z) ≤24 atomic%, and 0 atomic% ≤a≤10 atomic%, 0 atomic% ≤b≤5 atomic%, atomic% is atomic%, and [impurity] is atomic% of ancillary impurities. And A is any inclusion that is at least one element selected from Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta and W, and X. Is any inclusion that is at least one element selected from Re, Y, Zn, As, In, Sn and rare earth elements, and the total content of Nb, Zr, Ta and Hf in the composition of the alloy is The ribbon of the nanocrystalline alloy, which is less than 0.3 atomic percent and is heat-treated, contains nanocrystals of average particle size less than 40 nm dispersed in an amorphous matrix and is heat-treated. It has a local structure that occupies more than 30 volume percent of the ribbon of the nanocrystalline alloy, the magnetic core has a coercive force of less than 4 A / m, and after the heat treatment, the heat-treated nanocrystals. Winding a quality alloy ribbon, thereby forming a wound magnetic core,
including,
The method.

A magnetic core containing a ribbon of a nanocrystalline alloy having a composition represented by, wherein 0.6 atomic% ≤ x <1.2 atomic%, 10 atomic% ≤ y ≤ 20 atomic%, 0 atomic% < z ≤ 10 atomic%, 10 atomic% ≤ (y + z) ≤ 24 atomic%, and 0 atomic% ≤ a ≤ 10 atomic%, 0 ≤ b ≤ 5, atomic% is atomic percent, and [impurity] is The amount of ancillary impurities in atomic%, and A is selected from Ni, Mn, Co, V, Cr, Ti, Zr, Nb, Mo, Hf, Ta, W, P, C, Au and Ag. Any inclusion that is at least one element, and X is any inclusion that is at least one element selected from Re, Y, Zn, As, In and rare earth elements, and in the composition of the alloy. The total content of Nb, Zr, Ta and Hf is less than 0.3 atomic percent.
The nanocrystalline alloy ribbon contains nanocrystals with an average particle size of less than 40 nm dispersed in an amorphous matrix and contains more than 30 volume percent of the nanocrystalline alloy ribbon. Has a local structure that occupies
The magnetic core has a coercive force of less than 4 A / m.
The above magnetic core. The nanocrystalline alloy ribbon was heat-treated at a heating rate of 10 ° C./sec or higher for less than 30 seconds at a temperature in the range of more than 450 ° C. and up to 550 ° C., and was 1 MPa during the heat treatment. 25. The method of claim 25, wherein a tension of between 500 MPa is applied and the nanocrystalline alloy ribbon is wound after the heat treatment to form a wound magnetic core. The magnetic core is further heat-treated in a wound form for 1.8 ks (kiloseconds) to 10.8 ks at a temperature of 400 ° C. to 500 ° C. in a magnetic field of less than 4 kA / m applied along the circumferential direction of the magnetic core. 27. The method of claim 27. The nanocrystalline alloy ribbon is heat treated from room temperature to a predetermined holding temperature at an average heating rate greater than 10 ° C./sec, where the predetermined holding temperature exceeds 450 ° C. and is less than 550 ° C. , and the and the retention time is less than 30 seconds, the method of claim 27. The nanocrystalline alloy ribbon is heat treated from 300 ° C. to a predetermined holding temperature at an average heating rate greater than 10 ° C./sec, at which time the predetermined holding temperature exceeds 450 ° C. and 520 ° C. 27. The method of claim 27, which is less than and has a retention time of less than 30 seconds. 30. The method of claim 30, wherein the retention time is less than 20 seconds.

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